Catalytic carbon monoxide hydrogenation



. process for the production United States Patent Patented Sept. 3, 1957 fiice CATALYTIC CARBON 'MONOXIDE HYDRO GENATION N Drawing. Application November Serial N0. 394,195

Claims priority, application Germany August.10,.1 950 7 Claims. (Cl. 269-4496) This invention relatesto new and'useful improvements in catalytic carbon'monoxide hydrogenation, and isacontinuation-in-part of U. S. applicationiSerialNo. 239,844, filed August 1, 1951, now abandoned. The invention more particularly relates to the catalytic hydrogenation of carbon monoxide with the formation of synthesis products having a high content of oxygen-containing compounds.

The catalytic hydrogenation of carbon monoxide using fixed bed iron, cobalt, or nickel synthesis catalysts, is well known. The catalysts for this synthesisgenerally have a particle size of between 3 and 5 mm. and the synthesis product, which predominantly consists of hydrocarbons, may also contain small amounts of oxygenated compounds. Though synthesis catalysts having a particle size of less than 3 mm. diameter have incidentally been suggested for the production of hydrocarbons, it was found in practice in most cases that no additional eifect with regard to conversion yield and quality of the synthesis products could be obtained with the use of these smaller catalyst granules. Further, since the smaller catalyst granules when operating in the fixed bed process could cause an increased pressure loss, it was generally believed that catalysts having a particle size above 3 mm. diameter would be most desirable. In the so-called fluidized synthesis process, as opposed to -the fixed bed process, it is known to use catalysts having particle sizes of less than approximately 0.5 mm. and preferably of less than 0.2 mm. 'in diameter. The problems encountered in the fluidized process are, however, difierent from those encountered in the fixed bed process, and catalysts of this small grain size are required, ,so that the same will be fluidized by the upwardly flowing synthesis gas stream. In the fluidized state, the catalyst particles are suspended and eddied in the upwardly flowing gas stream and assume a liquid-like structure which afiords an extremely good removal of the reaction heat. If in the fluidized process catalyst particles having a considerably larger diameter would be used, the same could not be maintained in the suspended fluidized state with the gas velocities required for the carbon monoxide hydrogenation. When using iron catalysts in fluidized operation, the maximum particle size allowable for trouble-free operation is approximately 0.3-0.5 mm.

In a special synthesis process known as the synol of synthesis products having a high content of oxygenated compounds, catalysts having a small particle size of 1-2 mm. have been used. These catalysts are formed from pure electrolytic iron or iron from iron carbonyl. The iron is oxidized, mixed with small amounts of alumina and very small amounts of alkali amounting to O.15-0.5% K20 referred to the iron, melted, the melt broken into 1-2 mm. particles, and these particles reduced.

One object of this invention is the catalytic hydrogenation of carbon'monoxide'with production of synthesis products containing at least 30% and preferably more than 45% of oxygenated compounds. This, and still further objects, will become apparent from the following description:

In accordance wit-h the invention, the synthesis "isef fected at pressures ranging above I5 atmospheres and preferably above ldatmospheres with the use of tfixe'd bed iron catalysts. The catalysts used in accordance with the-invention, eontain-at-l'east 5%., and preferably -5-8.5 of alkali calculated-at K20 and referred to-the-iron present, and have a particle size-below 2 mm. and preferably between 0.5 andr1.9- mm. The range of-particle size of the catalysts is kept as narrow as possibleyand the catalyst, prior to contacting Wlthfl'IB-CaIbOH monoxide hydrogen-containingsynthesis gas, is reduced with reduction gas at flow velocities of at .least- 60 cm. per second, calculatedunder normal conditions, *an'd'a-t temperatures of between-200350-C.

.As compared with .the use of larger catal-yst grains, :it is possible, in accordance withthe-invention, to considerably decrease .the synthesis temperature, thereby favorably influencing the lite and activity of thecatalyst as well as reducingthe methane formation. Variations in the range of the .particle size should be maintained as narrow as possible. The more uniform -theiparticle size of the catalyst used, the more favorable the effects obtained in the'synthesis. a 1

By using the .catalysts :having .aparticle-size below 2 mm. with arelatively narrow rangein particle size variation, a surprising .and considerable increaseLin-the formation ofoxygenated compounds andpreferablyalcoholsis .etfected .as compared with 'the use-of catalysts 'of the same composition, .but with a particle size in excess 0f 2 mm. in diameter. .Particlesizesof below 0:5 mmph-ave not proved suitable .in practice since the gas ;passage through the catalyst layer is difllcult when using catalyst particles of this size which are partially present in the form :ofdust. Theprocess according to thetinvention is with [particular advantage effected with the use-of catalyst particle sizes of 0.5-1 mm. Particle sizes of 1.0- 1.5 mm. are also suitable. 'The particle size desired is obtainedbyusingcorresponding sieves.

Very surprisingly, this elfectof'an increase in-thecoritent of -oxygen-compounds caused by the use 'of catalysts having a particle size below 2mm, is "specific to-catalysts which contain 'at least 5% and preferably '5-8.'5% *of alkali calculated as K20 and referring to the iron content. a low alkalicontent, as,-for example, 0.15%-0.5% K20, this effect will no'toccur, or will only occur to'a ,very minor extent. 'Alk'ali contents in excess 'of 15% K20 show no'advantages. The process has particularly iniproved with the use-of sodium and potassium as alkali metals. However, it'isnot limited to the use of'these alkalim'etals.

An alkaliconte'nt of at least 5%, and preferably 5- 8.5% alkali calculated 'as K20 means that an amount of the particular alk-ali'useds'hould be present in the catalyst which is equivalent to at'lea'st 5%, and preferably "5- 8. by weight of K20 with respect to the iron content of the catalyst. g

"In accordance with the invention, 't-he synthes islshould be effected at super-atmospheric pressures, preferably be tween 10 and 70 atmospheres pressure. It is, however, possible to use higher synthesis pressures. The synthesis may be effected at temperatures between and about 300 C. and preferably jo'f180'-'250 C.

The synthesis, in accordance with the invention, should beetfected with a gas load of the catalyst of about liters up to more than 1000 liters of gas per liter of catalyst per hour. Gas loads o'f above 2000 1iter's per If, for example, catalysts are used which have liter of catalyst per hour have been found to be of little advantage. It is preferable to operate with a recycling of the synthesis gas with a portion of the tail gas being returned to the synthesis reactor. In this manner, a considerably more uniform heat removal may be obtained than with a straight gas passage. Most favorable opera? tion is obtained with a recycle ratio of 1 part by volume of fresh gas to 2-4 parts by volume of recycle gas.

It is of advantage, and particularly when using catalysts having a particle size of about 0.5-1 mm. diameter to pass the synthesis gas upwardly through the reactor. Obstructions of the catalyst tubes may incidentally occur when using the small particle size in accordance withthe invention when passing the gas in the conventional downward direction. These difiiculties may be overcome without changing the synthesis properties of the catalystby conducting the gas stream upwardly through the fixed bed catalysts. l

The preparation of'the catalysts in accordance with the invention, having a diameter of less than 2 mm. may be effected in any manner. If precipitated catalysts are used, for example, the catalysts may be precipitated from aniron salt solution such as an iron nitrite solution with the use of boiling alkali. The moist catalyst mass can then be molded into the desired particle size by means of devices known per se, as, for example, by means of a straining sieve. This method of molding may also be used with catalysts which are produced by the decomposition of metal compounds, as, for example, nitrates.

Fused and sintered catalysts may also be used in accordance with the invention. These catalysts are mechanically crushed to the desired particle size and then sieved.

It is of prime importance in the production of the catalysts in accordance with the invention that the reduction be eifected with high reduction gas flow velocities of at least 60 cm. per second, measured linear and under conditions of normal temperature and pressure, and preferably 60-150 cm. per second, and at temperatures between 200 and 350 C. Hydrogen, mixtures of hydrogen and carbon monoxide, and carbon monoxide alone and preferably hydrogen-rich gases or hydrogen alone are used as reduction gases.

The following examples are given by Way of illustration and not limitation:

Example 1 A catalyst containing 100 parts by weight of iron (Fe), 5 parts by-wtof copper (Cu), parts by wt. of calcium oxide (CaO) and 10 parts by wt. of kieselguhr was prepared by precipitation from a solution of corresponding metal nitrates by means of boiling soda solution. After the precipitation, the pH value was 9.2. The precipitated mass was immediately thereafter given into a filter press and filtered off from the mother liquor. The filter cake was partially Washed with distilled water (condensed water) to a residual alkali content which, calculated as K20 and referring to the iron content, amounted to 8.5% K20. The partially washed mass was predried to a residual water content of 60% H2O} and molded to granules of 1.9 mm., 3.1 mm., and 5 mm; diameter, respectively, by means of an extruding press of usual construction. The catalyst granules were reduced at 300 C. with hydrogen in such a manner that 80% of their iron content was present in the form of metallic The reduced catalysts, separated by individual particle sizes, were filled into three separate synthesis tubes. These synthesis tubes consisted of a double tube with the annular space between the tubes having a width of 10 mm; The length of the double tubes was 4.5 m. In all of the three tubes the synthesis was effected in such a manner that 150 parts by volume of water gas per part by volume of catalyst were hourly charged, and, moreover, 2.5 parts by volume of tail gas were admixed for every part by volume of fresh gas. The synthesis pressure was 10 kilos per square cm; l

AFTER AN OPERATINGTIIVIE OF 300 HOURS Synthesis CO'i'Hg Oxygenated Methane Catalyst particle tempera- Oonvercompounds, formation,

size, mm. ture, C. siou, Per- Percent Percent cent Examplev 2 A catalyst consisting of 100 parts by weight of iron (Fe), 5 parts by Weight of copper (Cu), 10 parts by Weightof kieselguhr, and 5 parts by weight of K20 (added in the form of KzCOslwas prepared in four difierent grain sizes of 0.5-1 mm, 1-2 mm, 2-3 mm. and 3-4 mm. The reduction of the catalyst was carried out at about 300 C. Withhydrogen at high gas velocities (1.5 m. per second) until the catalyst contained 80% of its iron content in the form ofmetallic iron. A comparison was made between these four catalysts at a gas load of hourly 1000 parts by volume of gas per part by volume of catalyst and at a synthesis pressure of 200 kilos per square cm. with straight gas passage.

After an operating time of 200 hours, the following results were obtained at 218 C.:

CO-i-Hz 00 con- Particle size, mm. converversion,

I stop, pcrpercent cent ' all with the catalyst grains of'a size of more than 2 mm.

in spite of a further temperature increase'by approximately 30 C., a good CO conversion over an extended period of time could be obtained with the 1 -2 mm. particles, and primarily with the 0.5-1 mm. particles, at temperatures of approximately 10-15 C. in excess of those mentioned above.

Working up of the synthesis product formed showed that the yield ofoxygenated compounds obtained with the 0.5-1 mm. particles was about 20 percent higher than that obtained with the 2-3 and 3-4 mm. particles.

I claim; l

1. In; the process for the catalytic hydrogenation of carbon monoxide, the improvement which comprises passing a carbon monoxide hydrogen containing synthesis gas at a-pressure above 5 atmospheres in contact with a fixed bed of precipitated iron catalyst obtained by precipitation from whom salt solution having a particle size of 0.5-1.9 mm. diameter and an alkali content of 5-15 parts alkali, calculated as K20 per parts by weight iron, said catalyst being reduced at a temperature between 200 and 350 C. with linear gas flow velocities of at least 60cm. per second measured cold, and recovering synthesis products containing at least 30% oxygenated compounds.

2. Improvement according to claim 1, in which said catalyst has a substantially uniform particle size.

3. Improvement according to claim 1, in which said contacting is effected at a pressure above 10 atmospheres.

4. Improvement according to claim 1, in which said catalyst contains 5 to 8.5 parts alkali calculated as K20 per 100 parts by weight iron.

5. Improvement according to claim 1, in which said catalyst has a particle size between 0.5 and 1.0 mm. diameter.

6. Improvement according to claim 1, in which said contacting is effected with a catalyst load of at least 10 liters of gas per liter of catalyst per hour.

7. Improvement according to claim 1, in which said contacting is eifected by passing synthesis gas upward through the catalyst bed.

2,560,344 Hemminger July 10, 1951 2,567,296 Milligan et al. Sept. 11, 1951 2,660,599 Rottig Nov. 24, 1953 2,698,335 Sumerford Dec. 28, 1954 FOREIGN PATENTS 528,617 Great Britain Nov. 1, 1940 OTHER REFERENCES Storch: The Fischer-Tropsch and Related Synthesis,

15 John Wiley & Sons, New York, 1951, pages 288 and 289. 

1. IN THE PROCESS FOR THE CATALYTIC HYDROGENATION OF CARBON MONOXIDE, THE IMPROVEMENT WHICH COMPRISES PASSING A CARBON MONOXIDE HYDROGEN CONTAINING SYNTHESIS GAS AT A PRESSURE ABOVE 5 ATMOSPHERES IN CONTACT WITH A FIXED BED OF PRECIPITATED IRON CATALYST OBTAINED BY PRECIPITATION FROM AN IRON SALT SOLUTION HAVING A PARTICLE SIZE OF 0.5-1.9 MM. DIAMETER AND AN ALKALI CONTENT OF 5-15 PARTS ALKALI, CALCULATED AS K2O PER 100 PARTS BY WEIGHT IRON, SAID CATALYST BEING REDUCED AT A TEMPERATURE BETWEEN 200 AND 350*C. WITH LINEAR GAS FLOW VELOCITIES OF AT LEAST 60 CM. PER SECOND MEASURED COLD, AND RECOVERING SYNTHESIS PRODUCTS CONTAINING AT LEAST 30% OXYGENATED COMPOUNDS. 